Catalyst composition comprising a heteropoly acid, zinc, and a support component and processes therefor and therewith

ABSTRACT

A process of contacting at least one isoparaffin and at least one C 5  olefin in the presence of a catalyst composition under conversion conditions to provide for converting the at least one isoparaffin and the at least one C 5  olefin is provided. The catalyst composition contains a heteropoly acid, zinc, and a support component.

BACKGROUND OF THE INVENTION

The present invention relates to a process of contacting an isoparaffinand a C₅ olefin in the presence of a catalyst composition.

Numerous catalysts have been disclosed in the prior art as suitable forcontacting isoparaffins and olefins containing from about 4 to about 7carbon atoms per molecule to provide for various converting of suchhydrocarbons, particularly to form hydrocarbon products having fromabout 6 to about 9 carbon atoms per molecule. Hydrocarbons having fromabout 6 to about 9 carbon atoms have various significant uses, such asincreasing the octane of gasoline, improving the distillation index ofgasoline, and to provide various oligomeric products that are valuablein either the petrochemical field, the fuel industry, or combinationsthereof. However, there is a significant and continuing need to providecatalyst compositions that are useful in increasing the number ofhydrocarbons having from about 6 to about 9 carbon atoms per moleculeproduced from the contacting of isoparaffins and olefins having fromabout 4 to about 7 carbon atoms per molecule.

Numerous catalysts and processes have also been disclosed in the priorart for isomerizing olefins, such as 1-pentene to 2-pentene. The isomerproducts can be utilized as additional feed stocks for alkylation units,various chemical processes, and the like. However, there is asignificant and continuing need to provide catalyst compositions thatare effective in providing for an increase in the yield of isomerproducts produced from isomerizing olefins.

It is also known in the art that a catalyst composition containingplatinum can be utilized for various hydrocarbon reactions andconversions, such as isomerizing, oligomerizing, disproportionating,cleaving, and the like and combinations thereof. However, there is asignificant expense associated with the use of platinum on suchcatalysts. Thus, catalyst compositions that do not utilize platinum, butwhich can provide for hydrocarbon production and regenerability similarto platinum-containing catalyst compositions would be of significantcontribution to the art and the economy.

It is also known in the art that the use of supported platinum catalystcompositions (such as platinum on alumina) for various hydrocarbonconversion reactions, such as isomerizing hydrocarbons, encountersignificant problems with the rapid deactivation of such catalystcompositions. There are believed to be a number of causes of suchcatalyst deactivation. One such cause of catalyst deactivation is theformation and accumulation of high molecular weight hydrocarbons, suchas C₅ to C₁₆ hydrocarbons, carbon, and/or coke, within the pores of suchcatalyst compositions, particularly at the reaction sites, also referredto as acid sites, within such catalyst compositions as well as on thesurface of such compositions. The formation and accumulation of suchhigh molecular weight hydrocarbons causes a high rate of catalystdeactivation, a short run life of the catalyst, and an unsteady yield ofhydrocarbon products. Hydrocarbon conversion reactions and processesthat counteract such deactivation would also be of significantcontribution to the art and the economy.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a process forcontacting at least one isoparaffin and at least one C₅ olefin in thepresence of a catalyst composition under conversion conditions toprovide for converting the at least one isoparaffin and the at least oneC₅ olefin. The converting can include, but is not limited to,isomerizing, oligomerizing, disproportionating, cleaving, and the likeand combinations thereof The catalyst composition comprises a heteropolyacid, zinc, and a support component.

Another object of the present invention is to provide a process thatcomprises contacting at least one isoparaffin and at least one C₅ olefinin a hydrocarbon-containing fluid in the presence of a catalystcomposition under conversion conditions to provide a product comprisinga larger amount of hydrocarbons having from about 6 to about 9 carbonatoms per molecule than were present in the hydrocarbon-containing fluidbefore such contacting.

Another object of the present invention is to provide a process thatcomprises contacting at least one isoparaffin and at least one C₅ olefinin the presence of a catalyst composition, during which such process,deactivation of such catalyst composition occurs, and such processfurther includes the addition of an organic chloride compound that isuseful in countering the deactivation of such catalyst composition.

A further object of the present invention is to provide a method bywhich the activity or run life of a catalyst composition comprising aheteropoly acid, zinc, and a support component can be enhanced, oressentially prolonged, resulting in a substantially constant conversionof hydrocarbons.

An embodiment of the present invention comprises a process comprisingcontacting at least one isoparaffin and at least one C₅ olefin in thepresence of a catalyst composition under conversion conditions toprovide for converting the at least one isoparaffin and the at least oneC₅ olefin, where the converting can include isomerizing, oligomerizing,disproportionating, cleaving and the like and combinations thereof. Acatalyst composition of the present invention comprises a heteropolyacid, zinc, and a support component.

Another embodiment of the present invention comprises a catalystcomposition comprising a heteropoly acid, zinc, and a support component.Such catalyst composition can be utilized in a variety of conversionprocesses such as contacting at least one isoparaffin and at least oneC₅ olefin, where the converting can include isomerizing, oligomerizing,disproportionating, cleaving, and the like and combinations thereof.

A process and catalyst composition of the present invention can offerseveral benefits, including, but not limited to, (1) the ability toconduct a variety of conversion reactions to provide for hydrocarbonshaving from about 6 to about 9 carbon atoms per molecule; (2) theability to obtain conversions and regenerability similar to aplatinum-containing catalyst composition; (3) extending the run life ofthe catalyst, which translates into longer operating runs betweencatalyst regenerations; and (4) fewer catalyst regeneration cycles,which translates into safer operation, less down time, and greatereconomic benefit.

Other objects and advantages of the present invention will becomeapparent from the detailed description and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to assist the understanding of the present invention, referencewill now be made to the appended drawings. The drawings are exemplaryonly and should not be construed as limiting the present invention.

FIG. 1 is a graph of the C5=conversions before the first regeneration ofcatalyst composition C described herein in Example 1 utilizing theconditions described herein in Example 3 and based on the data disclosedin Table 3.

FIG. 2 is a graph of the C5=conversions after the first regeneration ofcatalyst composition C described herein in Example 1 utilizing theconditions described herein in Example 3 and based on the data disclosedin Table 4.

FIG. 3 is a graph of the C5=conversions after the second regeneration ofcatalyst composition C described herein in Example 1 utilizing theconditions described herein in Example 3 and based on the data disclosedin Table 5.

FIG. 4 is a graph of the C5=conversions with no organic chloridecompound addition utilizing catalyst composition D described herein inExample 1 utilizing the conditions described herein in Example 4 andbased on the data disclosed in Table 7.

FIG. 5 is a graph of the C5=conversions with a 20 microliter per hourorganic chloride compound addition utilizing catalyst composition Ddescribed herein in Example 1 utilizing the conditions described hereinin Example 4 and based on the data disclosed in Table 8.

FIG. 6 is a graph of the C5=conversions with 40 microliter per hourorganic chloride compound addition utilizing catalyst composition Ddescribed herein in Example 1 utilizing the conditions described hereinin Example 4 and based on the data disclosed in Table 9.

DETAILED DESCRIPTION OF THE INVENTION

It has been discovered that a catalyst composition comprising aheteropoly acid, zinc, and a support component can be utilized in aprocess of the present invention comprising contacting at least oneisoparaffin and at least one C₅ olefin under conversion conditions toprovide for converting the at least one isoparaffin and the at least oneC₅ olefin. The converting can include, but is not limited to,isomerizing, oligomerizing, disproportionating, cleaving, and the likeand combinations thereof.

The term “C₅ olefin” as used herein refers to an olefin having 5 carbonatoms per molecule. The C₅ olefins that can be utilized in a process ofthe present invention include any C₅ olefins that can be contacted withat least one isoparaffin, according to a process of the presentinvention. Examples of suitable C₅ olefins include, but are not limitedto, 1-pentene, 2-methyl-1-butene, 2-methyl-2-butene, and the like andcombinations thereof. Preferably, the C₅ olefin comprises 1-pentene,2-methyl-2-butene, and combinations thereof. More preferably, the C₅olefin comprises 1-pentene.

Isoparaffins, also referred to as isoalkanes, that can be utilized in aprocess of the present invention include any isoparaffin that can becontacted with at least one C₅ olefin according to a process of thepresent invention. Examples of suitable isoparaffins include, but arenot limited to, isoparaffins comprising from about 4 to about 7 carbonatoms per molecule. Examples of suitable isoparaffins that can becontacted with at least one C₅ olefin utilizing a process of the presentinvention include, but are not limited to, isobutane, isopentane,2,2-dimethylbutane, 2,3-dimethylbutane, 2-methylpentane,3-methylpentane, 2,2-dimethylpentane, 2,4-dimethylpentane,2,2,3-trimethylbutane, 3,3-dimethylpentane, 2-methylhexane,2,3-dimethylpentane, 3-methylhexane, 3-ethylpentane, and the like andcombinations thereof. Preferably, an isoparaffin contacted with at leastone C₅ olefin utilizing a process of the present invention comprisesisopentane.

Generally, the converting provides for a product comprising hydrocarbonshaving from about 4 to about 10 carbon atoms per molecule. Preferably,such converting provides for a product comprising hydrocarbons havingfrom about 6 to about 9 carbon atoms per molecule. Also preferred isthat the converting provides for a product comprising a larger amount ofhydrocarbons having from about 6 to about 9 carbon atoms per moleculethan were present before such contacting. A preferred convertingcomprises isomerizing at least one C₅ olefin comprising 1-pentene toprovide for an isomer product comprising at least one 2-pentene.

The term “fluid” as used herein refers to gas, liquid, vapor, andcombinations thereof.

The term “zinc” as used herein refers to zinc in any form includingelemental zinc, a zinc component as described herein, or combinationsthereof.

Preferably, contacting at least one isoparaffin and at least one C₅olefin in the presence of a catalyst composition utilizing a process ofthe present invention provides for a converting of the at least oneisoparaffin and the at least one C₅ olefin. The term “converting” or“conversion” as used herein refers to any change in a hydrocarbon asdescribed herein as a result of utilizing a process of the presentinvention. Examples of suitable converting or conversion include, butare not limited to, isomerizing, oligomerizing, disproportionating,cleaving, and the like and combinations thereof. The converting of atleast one isoparaffin and at least one C₅ olefin according to a processof the present invention can include a variety of conversion reactionsthat can provide for a variety of hydrocarbon products. It should beunderstood that the various reactions can be occurring separately,simultaneously, and combinations thereof.

Generally, the reactants comprising at least one isoparaffin and atleast one C₅ olefin are initially present in a hydrocarbon-containingfluid. However, an additional embodiment of a process of the presentinvention includes separate feed streams comprising a feed streamcomprising at least one isoparaffin, such as a feed stream rich inisoparaffins, and a separate feed stream comprising at least one C₅olefin, that can be fed separately into a reactor and subjected tomixing in the presence of a catalyst composition of the presentinvention and for converting as described herein. Examples of suitablehydrocarbon-containing fluids include, but are not limited to, fuel gas,gasolines from catalytic oil-cracking (e.g., FCC and hydrocracking)processes, pyrolysis gasolines from thermal hydrocarbon-(e.g., methane,propane, naphtha) cracking processes, naphthas, gas oils, reformates,straight-run gasoline, and the like and combinations thereof.

A heteropoly acid of a catalyst composition of the present invention canbe any heteropoly acid that can be utilized to provide a catalystcomposition that can be utilized in a process of the present invention.Generally, a heteropoly acid comprises a class of acids formed by thecondensation of two or more inorganic oxyacids. For example, phosphateand molybdenum ions, when reacted in an acidic medium, are condensed toform 12-molybdophosphoric acid, a typical heteropoly acid. A widevariety of elements ranging from Group I to Group VIII of the PeriodicTable of the Elements can become the central atom of the heteropoly acidanion, also referred to as the heteroatom, (e.g., phosphorus, in thecase of 12-molybdophosphoric acid). The nature of the heteroatom is agoverning factor that determines both the condensation structure and thephysical properties of the heteropoly acid. Atoms coordinated to theheteroatom via oxygens are called polyatoms, also referred to as thecoordinating element, (e.g., molybdenum, in the case of12-molybdophosphoric acid) and in most cases are any of one of suchlimited species as molybdenum, tungsten, niobium, and vanadium. Aparticular class of heteropoly acids is the protonated form ofheteropolymolybdates. These anions contain from 2 to about 18 hexavalentmolybdenum atoms around one or more central atoms. Another class ofheteropoly acids, which is analogous to the protonated form ofheteropolymolybdates, is the protonated form of heteropolytungstates. Inheteropolytungstates, the polyatom or coordinating element is tungsten,instead of molybdenum. Examples of a suitable heteropoly acid include,but are not limited to, 12-molybdophosphoric acid, 12-tungstophosphoricacid, molybdosilicic acid, 12-tungstosilicic acid, and the like andcombinations thereof. Preferably, a heteropoly acid is12-molybdophosphoric acid.

A support component of a catalyst composition of the present inventioncan be any support component that suitably provides for a catalystcomposition of the present invention that can be utilized in a processof the present invention. A support component of a catalyst compositionof the present invention can be any inorganic metal oxide that istypically used as a catalytic support material. Examples of a suitablesupport component include, but are not limited to, alumina, silica,aluminasilicates, activated carbon, zeolites, oxides of the metals ofGroups II, III, IV, V, and VI A of the Periodic Table of the Elements,and the like and combinations thereof. The oxides of the metals ofGroups II, III B and IV B of the Periodic Table of the Elements arepreferred, such as alumina, boria, zinc oxide, magnesia, calcium oxide,strontium oxide, barium oxide, titania, zirconia, vanadia, and the likeand combinations thereof. The support component can be syntheticallyprepared or can be a naturally occurring support material, such asnaturally occurring clays, kieselguhr, diatomaceous earth, zeolites,silica, thoria, zirconia, and the like and combinations thereof.Preferably, a support component of a catalyst composition of the presentinvention comprises alumina.

Alumina suitable for use in a catalyst composition of the presentinvention can be characterized by having the following characteristics.Generally, the surface area of the alumina is in the range of from about5 m²/g (measured by the Brunauer, Emmett, Teller method, i.e., BETmethod) to about 400 m²/g, preferably in the range of from about 10 m²/gto about 300 m²/g, and more preferably in the range of from about 50m²/g to about 200 m²/g. The pore volume of the alumina is generally inthe range of from about 0.05 mL/g to about 2 mL/g, preferably in therange of from about 0.10 mL/g to about 1.5 mL/g, and more preferably inthe range of from about 0.20 mL/g to about 1 mL/g. The average porediameter of the alumina is generally in the range of from about 5angstroms to about 600 angstroms, preferably in the range of from about10 angstroms to about 500 angstroms, and more preferably in the range offrom about 25 angstroms to about 200 angstroms.

The size and shape of a catalyst composition of the present inventionwill be based largely on the size and shape of the support component.Preferably, a catalyst composition of the present invention is in theform of tablets, pellets, extrudates, spheres, and the like andcombinations thereof. More preferably, the catalyst composition of thepresent invention is in the form of an extrudate comprising a heteropolyacid, zinc, and a support component, preferably alumina. A catalystcomposition of the present invention generally has a particle size inthe range of from about 0.1 millimeters (mm) to about 10 mm, preferablyin the range of from about 0.5 mm to about 8 mm, and more preferably inthe range of from about 1 mm to about 6 mm.

A zinc component of the present invention can be any zinc component thatsuitably provides for a catalyst composition of the present inventioncomprising zinc that can be utilized in a process of the presentinvention. Generally, this will be a reducible zinc salt or zinc oxide.Examples of a suitable zinc component include, but are not limited to,zinc bromide, zinc chloride, zinc iodide, zinc nitrate hydrate, zincnitrate hexahydrate, zinc nitrate, zinc oxide, zinc perchloratehexahydrate, zinc sulfate heptahydrate, and the like, and combinationsthereof. A preferred zinc component that can be utilized in preparing acatalyst composition of the present invention comprises zinc chloride.It should be understood that the zinc component may be partially orcompletely converted to elemental zinc during a process of preparing orusing a catalyst composition of the present invention.

An amount of zinc component utilized in a process of preparing acatalyst composition of the present invention is such as to provide aconcentration of zinc in a catalyst composition of the present inventionthat can be utilized in contacting at least one isoparaffin and at leastone C₅ olefin according to a process of the present invention. An amountof zinc component utilized in preparing a catalyst composition of thepresent invention is such as to provide a concentration of zinc in acatalyst composition of the present invention generally in the range offrom about 0.1 weight percent to about 10 percent based on the totalweight of the catalyst composition, preferably in the range of fromabout 0.5 weight percent to about 8 weight percent, and more preferablyin the range of from about 1 weight percent to about 6 weight percent.

An amount of support component utilized in a process of preparing acatalyst composition of the present invention can be any amount thatsuitably provides for a catalyst composition of the present inventionthat can be utilized in contacting at least one isoparaffin and at leastone C₅ olefin according to a process of the present invention. An amountof support component, preferably alumina, utilized in preparing acatalyst composition of the present invention is such as to provide aconcentration of support component in a catalyst composition of thepresent invention generally in the range of from about 50 weight percentto about 99.9 weight percent based on the total weight of the catalystcomposition, preferably in the range of from about 60 weight percent toabout 95 weight percent, and more preferably in the range of from about70 weight percent to about 90 weight percent.

An amount of heteropoly acid utilized in a process of preparing acatalyst composition of the present invention can be any amount thatsuitably provides for a catalyst composition of the present inventionthat can be utilized in contacting at least one isoparaffin and at leastone C₅ olefin according to the process of the present invention. Anamount of heteropoly acid utilized in a process of preparing a catalystcomposition of the present invention is such as to provide aconcentration of polyatom, preferably molybdenum, in a catalystcomposition of the present invention generally in the range of fromabout 0.1 weight percent to about 10 weight percent based on the totalweight of the catalyst composition, preferably in the range of fromabout 1 weight percent to about 10 weight percent, and more preferablyin the range of from about 1 weight percent to about 5 weight percent.It should be understood that during a process of preparing or using acatalyst composition of the present invention, the heteropoly acid maybe converted to the individual heteroatom(s) and polyatom(s).

A catalyst composition of the present invention can be prepared by anysuitable manner or method(s) that suitably provides for a catalystcomposition of the present invention. Generally, a process of preparinga catalyst composition of the present invention comprises contacting asupport component as described herein, preferably alumina, with aheteropoly acid and a zinc component as described herein. Examples ofsuitable contacting include, but are not limited to, impregnation,mixing, and the like in combinations thereof. Generally, contacting aheteropoly acid, a zinc component and a support component according toprocess of the present invention comprises any impregnation techniqueknown in the art such as incipient wetness impregnation, sprayimpregnation, and the like and combinations thereof. A preferredimpregnation technique is incipient wetness impregnation that includesessentially completely filling the pores of the support component,preferably alumina, with a solution of the heteropoly acid and asolution of the zinc component.

Preferably, the heteropoly acid is an aqueous solution and is preferablysoluble in water. The concentration of the heteropoly acid in thesolution can range upwardly to the solubility limit of the heteropolyacid in the solvent. Generally, a concentration of the heteropoly acidin the solution can be in the range of from about 1 weight percent toabout 99 weight percent, preferably in the range of from about 5 weightpercent to about 50 weight percent, and more preferably in the range offrom about 5 weight percent to about 25 weight percent. Generally, aweight ratio of support component to heteropoly acid is in the range offrom about 0.01:1 to about 20:1, preferably in the range of from about0.1:1 to about 10:1, and more preferably in the range of from about0.1:1 to about 5:1.

The solution of the zinc component may be an aqueous solution, analcohol-containing solution, or a hydrocarbon solution of the zinccomponent. It is preferred for the zinc component to be soluble inwater. The concentration of the zinc component in the solution can rangeupwardly to the solubility limit of the zinc component in the solvent.Generally, a concentration of the zinc component in the solution can bein the range of from about 1 weight percent to about 99 weight percent,preferably in the range of from about 5 weight percent to about 50weight percent, and more preferably in the range of from about 5 weightpercent to about 25 weight percent. Generally, a weight ratio of supportcomponent to zinc component is in the range of from about 0.01:1 toabout 20:1, preferably in the range of from about 0.1:1 to about 10:1,and more preferably in the range of from about 0.1:1 to about 5:1.

The heteropoly acid and zinc component as referred to herein can becontacted with a support component of the present invention in anysuitable manner so long as a catalyst composition of the presentinvention can be prepared. Generally, a support component is firstimpregnated with a zinc component dissolved in an aqueous solution suchas deionized water, by incipient wetness impregnation. The supportcomponent can also be sprayed with an impregnating solution containing adissolved zinc component. Generally, the concentration of the zinccomponent in the impregnating solution is in the range from about 0.1gm/mL to about 2 gm/mL, preferably in the range of from about 0.2 gm/mLto about 1 gm/mL. The presently preferred zinc component to be used inthe impregnating solution is zinc chloride. Examples of a suitablesolvent of the impregnating solution include, but are not limited to,deionized water, an alcohol as described herein, and the like andcombinations thereof. The amounts of zinc component utilized are amountssuitable to provide concentrations as described herein of zinc in acatalyst composition of the present invention. Examples of a suitablealcohol include, but are not limited to, methyl alcohol, ethyl alcohol,isopropyl alcohol, and the like and combinations thereof. A preferredimpregnating solution of a zinc component comprises zinc chloridedissolved in deionized water.

The support component impregnated with a zinc component can then beimpregnated with a heteropoly acid, preferably dissolved in an aqueoussolution, such as deionized water, by incipient wetness impregnation.The support component containing a zinc component can also be sprayedwith an impregnating solution containing a dissolved heteropoly acid.Generally, the concentration of the heteropoly acid in the impregnatingsolution is in the range of from about 0.1 gm/mL to about 2 gm/mL,preferably in the range of from about 0.2 gm/mL to about 1 gm/mL. Thepresently preferred heteropoly acid to be used in the impregnatingsolution is 12-molybdophosphoric acid. Examples of a suitable solvent ofthe impregnating solution include, but are not limited to, deionizedwater and the like and combinations thereof. The amounts of heteropolyacid utilized are amounts suitable to provide concentrations asdescribed herein of a polyatom, preferably molybdenum, in a catalystcomposition of the present invention. A preferred impregnating solutionof a heteropoly acid comprises a heteropoly acid dissolved in deionizedwater.

Other examples of a process of preparing a catalyst composition of thepresent invention include first impregnating a support component with asolution of heteropoly acid as described herein followed by a secondimpregnation of the support component and heteropoly acid with a zinccomponent as described herein. Preferably, a support component issimultaneously impregnated with a solution of a zinc component,preferably zinc chloride dissolved in deionized water, and a solution ofheteropoly acid, preferably 12-molybdophosphoric acid dissolved indeionized water.

In an example process of preparing a catalyst composition of the presentinvention, after contacting a support component with a heteropoly acid,preferably a solution of 12-molybdophosphoric acid, and a zinccomponent, preferably a solution of zinc chloride, the resulting mixturecomprising a heteropoly acid, a zinc component, and a support componentcan then be formed or shaped, preferably extruded or granulated. Anysuitable means known to those skilled in the art for forming, preferablyextruding, granulating, agglomerating, and the like and combinationsthereof, the mixture comprising a heteropoly acid, a zinc component anda support component can be used to achieve the desired formed mixture,preferably extruded mixture (i.e., extrudate), granulated mixture (i.e.,granulate), agglomerated mixture (i.e., agglomerate) and the like andcombinations thereof. Examples of suitable means for forming include,but are not limited to, means for extruding, means for granulating,means for agglomerating, and the like and combinations thereof. A liquidsuch as, but not limited to, water, may be used in forming, preferablyextruding, granulating, agglomerating, and the like and combinationsthereof, the mixture. Suitable means for extruding can include, but arenot limited to, such devices as screw extruders (also known as augerextruders or auger-type extruders) and the like.

Suitable means for granulating can include, but are not limited to, wetgranulation and dry granulation. Wet granulation comprises mixing dryingredients such as a heteropoly acid, a zinc component, and a supportcomponent with a liquid such as, but not limited to, water. Theresulting wet paste is then dried, coarsely ground, and sieved to thedesired size using the proper screen size. Dry granulation comprisesdensifying dry ingredients, such as a heteropoly acid, a zinc component,and a support component, in a heavy-duty tableting press to producegranulates which are subsequently crushed to the desired size.

It can be desirable for the formed mixture to be an agglomerate of themixture of a heteropoly acid, a zinc component and a support component.Any suitable means or methods known by those skilled in the art forforming such an agglomerate, i.e., means for agglomerating, can be used.Examples of suitable means for agglomerating include, but are notlimited to, molding, pressing, pelletizing, tumbling, densifying, andthe like and combinations thereof. Further discussion of such methods,including extruding means and granulating means, is provided in asection entitled “Size Enlargement” in Perry's Chemical Engineers'Handbook, Sixth Edition, published by McGraw-Hill, Inc., copyright 1984,at pages 8–60 through 8–72, which pages are incorporated herein byreference.

For example, the heteropoly acid, zinc component, and support componentcan be compounded and subsequently shaped (such as by pelletizing,extruding or granulating) into a compounded composition. Generally theparticle size of the compounded composition is in the ranges asdescribed herein.

A process of preparing a catalyst composition of the present inventionfurther comprises drying under a drying condition. A “drying condition”as referred to herein includes a temperature generally in the range offrom about 20° C. to about 90° C., preferably in the range of from about20° C. to about 80° C., and more preferably in the range of from about25° C. to about 70° C. A drying condition further comprises a pressuregenerally in the range of from about 0 pounds per square inch absolute(psia) to about 200 psia, preferably in the range of from about 1 psiato about 150 psia, and more preferably in the range of from about 2 psiato about 100 psia. A drying condition further comprises a time periodgenerally in the range of from about 0.5 hour to about 40 hours,preferably in the range of from about 0.5 hour to about 30 hours, andmore preferably in the range of from about 1 hour to about 20 hours. Adrying condition further comprises an atmosphere, suitable for drying asdescribed herein, preferably air.

In a preferred method of preparing a catalyst composition of the presentinvention, after contacting a heteropoly acid, a zinc component and asupport component as described herein, a mixture, preferably a paste,comprising such components is provided and can be subjected to a meansfor extruding as described herein to provide for a wet extrudatecomprising such components that is then subjected to drying under adrying condition as described herein to provide a dried extrudatecomprising such components that can then be subjected to a means forgranulating as described herein to provide for dried extrudate pelletscomprising a heteropoly acid, a zinc component and a support component.

While drying under a drying condition as described herein can providefor a catalyst composition of the present invention, a process ofpreparing a catalyst composition of the present invention can furthercomprise calcining under calcining condition. A “calcining condition” asreferred to herein includes a temperature generally in the range of fromabout 100° C. to about 500° C., preferably in the range of from about150° C. to about 250° C., and more preferably in the range of from about175° C. to about 225° C. A calcining condition further comprises apressure generally in the range of from about 0 pounds per square inchabsolute (psia) to about 750 psia, preferably in the range of from about1 psia to about 600 psia, and more preferably in the range of from about2 psia to about 500 psia. A calcining condition further comprises a timeperiod generally in the range of from about 0.5 hour to about 30 hours,preferably in the range of from about 1 hour to about 20 hours, and morepreferably in the range of from about 1 hour to about 10 hours. Acalcining condition further comprises an atmosphere selected from thegroup consisting of an oxygen-containing atmosphere (e.g., air),nitrogen, helium, argon, and the like and combinations thereof. Duringcalcining, substantially all volatile matter (e.g., water andcarbonaceous materials) is removed.

It should be understood that the processes of preparing a catalystcomposition of the present invention will depend, in part, on theinitial form and particle size of the support component. For example,when the support component comprises a powder form such as aluminapowder, the resulting mixture after contacting such alumina powder withsolutions of heteropoly acid and zinc component, will provide a pastethat can be subjected to a means for forming as described herein, suchas a means for extruding, to provide for a wet extrudate that can thenbe subjected to drying under a drying condition as described herein toform a dried extrudate that can then be subjected to another means forforming as described herein, such as a means for granulating, or othermethods for changing the size and shape of the dried extrudate into aform and particle size as described herein. Also, for example, when thesupport component is present in pellets, such as alumina pellets sizedfrom about 1 mm to about 10 mm, once such pellets are contacted with,preferably impregnated with, solutions of a heteropoly acid and a zinccomponent followed by drying under a drying condition as describedherein and, if desired, calcined under a calcining condition asdescribed herein, further shaping and sizing, such as by subjecting to ameans for forming as described herein, may not be needed as theresulting catalyst composition will have a size and shape similar to theinitial support component before impregnating.

A process of preparing a catalyst composition of the present inventionfurther comprises, after contacting a heteropoly acid, a zinc component,and a support component, according to a process of the presentinvention, activating under an activating condition that suitablyprovides for a catalyst composition that can be utilized in a process ofthe present invention for contacting at least one isoparaffin and atleast one C₅ olefin. An “activating condition” as referred to hereinincludes a temperature generally in the range of from about 50° C. toabout 500° C., preferably in the range of from about 60° C. to about400° C., and more preferably in the range of from about 70° C. to about300° C. An activating condition further comprises a pressure generallyin the range of from about 0 pounds per square inch absolute (psia) toabout 750 psia, preferably in the range of from about 1 psia to about500 psia, and more preferably in the range of from about 2 psia to about400 psia. An activating condition as referred to herein furthercomprises a time period generally in the range of from about 0.1 hour toabout 30 hours, preferably in the range of from about 0.5 hour to about20 hours, and more preferably in the range of from about 1 hour to about10 hours. An activating condition further comprises an atmospheresuitable for activating a catalyst composition of the present invention.Examples of a suitable activating atmosphere include, but are notlimited to, hydrogen, hydrogen diluted with nitrogen, ammonia,hydrazine, other reducing gases, and the like and combinations thereof.A preferred activating atmosphere is hydrogen. Also, a deactivatedcatalyst composition as described herein can be reactivated orregenerated by subjecting the deactivated catalyst composition to anactivating condition as described herein.

Another example of a suitable activating atmosphere comprises a mixtureof hydrogen and an organic chloride compound as described herein.Utilizing a mixture of hydrogen and organic chloride compound can beuseful when a conducting a process of the present invention utilizing anorganic chloride compound addition as described herein. Such mixture ofhydrogen and organic chloride compound can be useful to not onlyactivate the catalyst composition, but also to pretreat such catalystcomposition.

Generally, a process of the present invention is conducted in aconversion zone wherein is contained a catalyst composition of thepresent invention under conversion conditions that provide forcontacting at least one isoparaffin and at least one C₅ olefin toprovide for converting the at least one isoparaffin and the at least oneC₅ olefin. Conversion conditions include any temperature suitable forconducting a process of the present invention. Generally, the conversionconditions comprise a temperature in the range of from about 30° C. toabout 500° C., preferably in the range from about 40° C. to about 400°C., and more preferably in the range of from about 50° C. to about 300°C.

The conversion conditions further comprise a conversion pressure thatcan be any pressure sufficient to provide for a process of the presentinvention, comprising contacting at least one isoparaffin and at leastone C₅ olefin, and is generally sufficient to maintain the reactants andproducts substantially in the liquid phase. The conversion pressureswill generally be in the range of from about 40 pounds gauge pressureper square inch (psig) to about 1000 psig, preferably in the range offrom about 100 psig to about 750 psig, and more preferably in the rangeof from about 200 psig to about 500 psig. With all reactants in theliquid phase, increased pressure has no significant effect upon theconversion(s) of the present invention.

The conversion conditions further comprise a contact time for thehydrocarbon conversion(s) of a process of the present invention in aconversion zone in the presence of a catalyst composition of the presentinvention that can be any time period that suitably provides for aconversion process of the present invention. Generally, the contact timeis in the range from about from about 0.05 minute to about 2 hours,preferably in the range of from about 0.05 minute to about 60 minutes.

Generally, a weight ratio of catalyst composition to total hydrocarbonis any weight ratio that provides for a process of the presentinvention. Generally, a weight ratio of catalyst composition to totalhydrocarbon is in the range of from about 0.01:1 to about 20:1,preferably in the range of from about 0.5:1 to about 15:1, and morepreferably in the range of from about 1:1 to about 10:1.

A process of the present invention, comprising contacting at least oneisoparaffin and at least one C₅ olefin, can be carried out either as abatch or continuous type of operation, although it is preferred foreconomic reasons to carry out the process continuously. It has beengenerally established that in alkylation processes, the more intimatethe contact between the hydrocarbon-containing fluid, i.e., feedstock,and the catalyst, the better the quality of alkylate product obtained.With this in mind, a process of the present invention, when operated asa batch operation, is characterized by the use of vigorous mechanicalstirring or shaking of the reactants and catalyst composition.

The conversion zone design is not critical, except that sufficientdispersion of the hydrocarbon into the catalyst composition should beachieved under well-mixed conditions. A preferred reactor design is aplug-flow fixed bed reactor.

An example process of the present invention comprises contacting atleast one isoparaffin comprising isopentane and at least one C₅ olefinselected from the group consisting of 1-pentene, 2-methyl-1-butene,2-methyl-2-butene, and combinations thereof in the presence of acatalyst composition of the present invention under conversionconditions to provide at least one product hydrocarbon comprising fromabout 4 to about 10 carbon atoms per molecule, preferably comprisingfrom about 6 to about 9 carbon atoms per molecule. Preferably, the atleast one isoparaffin and the at least one C₅ olefin are present in ahydrocarbon-containing fluid and that the process provides for a productcomprising a larger amount of hydrocarbons comprising from about 6 toabout 9 carbon atoms per molecule than were present before thecontacting of at least one isoparaffin and at least one C₅ olefin. Theconverting can be selected from the group consisting of isomerizing,oligomerizing, disproportionating, cleaving, and the like andcombinations thereof.

One example converting that may occur during a process of the presentinvention comprises contacting at least one isoparaffin and at least oneC₅ olefin to provide for an intermediate hydrocarbon containing 10 ormore carbon atoms per molecule followed by subsequent converting, suchas, but not limited to, disproportionating or cleaving to provide forhydrocarbons having less than 10 carbon atoms per molecule, preferablyhaving from about 6 to about 9 carbon atoms per molecule. Anotherexample converting that may occur during a process of the presentinvention comprises oligomerizing where, during contacting of at leastone isoparaffin and at least one C₅ olefin according to a process of thepresent invention, two or more C₅ olefins may be dimerized to provide aproduct having 10 carbon atoms per molecule. Another example convertingthat may occur during a process of the present invention comprises atleast one C₅ olefin comprising 1-pentene that is isomerized, alsoreferred to as double bond isomerization, to provide a 2-pentene. Thevarious converting reactions as described herein may occur separately,simultaneously, and in combinations thereof during a process of thepresent invention.

A catalyst composition of the present invention may be added byinjection directly into a conversion zone, or may be mixed with ahydrocarbon-containing fluid containing at least one isoparaffin and atleast one C₅ olefin, or may be mixed with fresh and/or circulatingcatalyst composition, or with a stream of mixed hydrocarbon-containingfluid and catalyst composition, or the like and combinations thereof.Downstream from the conversion zone, the catalyst composition can bepreferably separated from the product stream, mixed with fresh and/orcirculating catalyst composition, and recycled to the conversion zone.The particular separation technique selected depends upon thecharacteristics of the catalyst composition and the desired reactionproducts. Selection of such separation techniques is within the skill inthe art.

Another example process of the present invention comprises separatinghydrocarbons containing 5 carbon atoms per molecule, such as C₅ olefins,from gasoline, routing the C₅ hydrocarbons to a conversion zonecomprising a reactor containing a catalyst composition of the presentinvention and separating the resulting products into a C₃/C₄ fractioncontaining hydrocarbons having from about 3 to about 4 carbon atoms, aC₅ fraction containing hydrocarbons containing 5 carbon atoms permolecule, and a C₆+ fraction containing hydrocarbons containing 6 ormore carbon atoms per molecule. The C₃/C₄ fraction can be sent to analkylation unit, the C₅ fraction can be recycled to the conversion zone,and the C₆+ fraction can be further separated into a gasoline rangefraction and a diesel range fraction. The diesel range product can behydrogenated to provide a blend stock with little to no sulfur, olefins,or aromatics.

During a process of the present invention, impurities present in thefeed stream(s) can contribute to a rapid decrease in catalyst activity.Such catalyst deactivating effect is counteracted in a process of thepresent invention by the presence of an additive comprising an organicchloride compound. An organic chloride compound suitable as an additivein a process of the present invention comprises any organic chloridecompound that helps deactivate or counter the effects of catalystdeactivation during a process of the present invention comprisingcontacting at least one isoparaffin and at least one C₅ olefin. Examplesof a suitable organic chloride compound include, but are not limited to,tetrachloroethylene (TCE) (also referred to as perchloroethylene orPCE), ethylaluminum dichloride, carbon tetrachloride, hexachloroethane,1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane,2-chloro-2-methylpropane, and the like and combinations thereof. Apreferred organic chloride compound comprises tetrachloroethylene. Amore preferred organic chloride compound comprises a combination oftetrachloroethylene and ethylaluminum dichloride. During a process ofthe present invention comprising contacting at least one isoparaffin andat least one C₅ olefin, the additive comprising an organic chloridecompound can be injected into the hydrocarbon-containing fluid, any ofthe individual feed streams, or combinations thereof.

An effective amount of an organic chloride compound, i.e., theconcentration of organic chloride compound, in a process of the presentinvention comprising contacting at least one isoparaffin and at leastone C₅ olefin is in the range of from about 0.01 ppm organic chloridecompound to about 1000 ppm organic chloride compound (i.e., about 0.01part by weight organic chloride compound per million parts by weight oftotal hydrocarbon to about 1000 parts by weight organic chloridecompound per million parts by weight of total hydrocarbon). Preferably,a concentration of organic chloride compound is in the range of fromabout 0.05 ppm organic chloride compound to about 900 ppm organicchloride compound, and more preferably in the range of from about 0.1ppm organic chloride compound to about 800 ppm organic chloridecompound. The amount of additive comprising an organic chloride compoundinjected into the hydrocarbon-containing fluid, any of the individualfeed streams, or combinations thereof, should be such that theconcentrations of the organic chloride compound recited herein can bemaintained. The injection of the organic chloride compound can beconducted continuously or intermittently, i.e., pulsed.

After a catalyst composition the present invention has been deactivatedby, for example, coke deposition, or feed poisons, to the extent thatthe fluid conversion and/or the production of hydrocarbons having from 6to 9 carbon atoms per molecule has become unsatisfactory, the catalystcomposition can be regenerated by, for example, calcining to burn offdeposited coke and other carbonaceous materials, such as oligomers orpolymers, preferably at a temperature in the range of from about 100° C.to about 500° C. The optimal time periods for calcining depend generallyon the types and amounts of the deactivating deposits on the catalystcomposition and on the calcination temperatures. These optimal timeperiods can be determined by those possessing ordinary skill in the artand are omitted herein for the interest of brevity. An exampleregeneration procedure comprises subjecting a deactivated catalystcomposition of the present invention to an activating under anactivating condition as described herein.

Another example regeneration procedure comprises subjecting adeactivated catalyst composition of the present invention to a hydrogentreatment comprising stopping the hydrocarbon-containing fluid feed,removing liquid hydrocarbon components from the conversion zone, andpurging with an inert gas for a time period in the range of from about0.01 hour to about 48 hours, preferably about 10 minutes. Thetemperature is then increased to about 300° F. to about 700° F.,preferably about 350° F. to about 550° F., and a flow of hydrogen isstarted to the conversion zone at a flow rate sufficient to achieve agas hourly space velocity in the range of from about 0.01 hours⁻¹ toabout 100 hour⁻¹ and the hydrogen flow over the catalyst composition ismaintained for a time period in the range of from about 0.01 hour toabout 48 hours, preferably about 2 hours to about 24 hours. Thetemperature can then be controlled to the desired conversion conditiontemperature as described herein and the hydrocarbon-containing fluidfeed can be reintroduced. In addition, after the flow of hydrogen isstopped, a flow of nitrogen can be started at a temperature of about300° F. to about 700° F., preferably about 350° F. to about 550° F., andat a flow rate sufficient to achieve a gas hourly space velocity in therange of from about 0.01 hour⁻¹ to about 100 hour⁻¹ and the nitrogenflow over the catalyst composition can be maintained for a period oftime in the range of from about 0.01 hour to about 48 hours, preferablyabout 2 hours to about 24 hours, before the reintroduction of thehydrocarbon-containing fluid feed. Also, the flow of hydrogen can besubstituted with a mixture of hydrogen and an organic chloride compoundas described herein. Substituting with such a mixture can be an optionwhen conducting a process of the present invention utilizing the organicchloride compound addition as described herein.

The following examples are presented to further illustrate the presentinvention and are not to be construed as unduly limiting the scope ofthe present invention. In the following Examples and Tables thefollowing abbreviations are used: C2 is ethane; C3 is propane; C3=ispropylene; iC4 is isobutane; iC4=is isobutene; 1C4=is 1-butene; nC4 isnormal butane; 2C4=t is trans-2-butene; NeoC5 is neopentane (i.e.,2,2-dimethylpropane); 2C4=c is cis-2-butene; 2C4=is total 2-butenes;3MB1 is 3-methyl-1-butene; iC5 is isopentane; iC5=is isopentene; 1C5=is1-pentene; 2MB1 is 2-methyl-1-butene; nC5 is normal pentane; C5=is totalpentenes; 2C5=t is trans-2-pentene; 2C5=c is cis-2-pentene; 2C5=is total2-pentenes; 2MB2 is 2-methyl-2-butene; ?C1–C5 is unidentified componentseluting in the C1–C5 (methane-pentane) region; C6–C8 is total componentshaving 6 to 8 carbon atoms per molecule without regard to the compoundtype (i.e., paraffins, olefins, aromatics, naphthenes, and the like); C9is total components having 9 carbon atoms per molecule regardless oftype; C6+ is total components with at least 6 or more carbon atoms permolecule regardless of type; C10+ is total components with at least 10or more carbon atoms per molecule regardless of type; Conv isconversion; Lights is total hydrocarbons having 4 or less carbon atomsper molecule; TOS is Time on Stream; Rxtr is reactor; Cl is organicchloride compound; TSP is Temperature Set Point; Temp. is temperature;and MoHPA is 12-molybdophosphoric acid. C6–C8, C9, C6+, and C10+ weredetermined by the relative retention times on a gas chromatograph columnthat allowed components to elute in the order of increasing boilingpoint. All numbers in the tables are weight percent unless otherwiseindicated.

EXAMPLE 1

Example 1 illustrates the preparation of several catalyst compositionsthat were subsequently tested as catalysts in a process comprisingcontacting an isoparaffin and a C₅ olefin.

Catalyst A: (MoHPA/Zeolite Beta/Pt) A solution of 3.80 grams of12-molybdophophoric acid in about 25 mL of distilled water was preparedand approximately half of the solution was added to a 17.0 gram quantityof zeolite beta (Si/Al ratio of 150) under incipient wetness conditions.A 1.20 gram quantity of a platinum (IV) chloride (PtCl₄) solution (10%Platinum) was then added to the remaining half of the aqueous12-molybdophophoric acid solution and then slowly added to the zeolitebeta. After addition, the resulting material was then was dried in avacuum oven at about 80° C. for about three hours to provide a finalweight of 20.42 grams. The resulting dried material was then mixed witha 2.5 gram quantity of bentonite clay filler and about 0.85 mL ofdistilled water to provide a paste that was extruded through a 25 mLplastic syringe. The resulting extrudate was then dried in a drying ovenat about 115° C. for about 18 hours. The resulting dried extrudate wasthen granulated to provide pieces of about 0.125 inches to about 0.25inches in length. A 9.99 gram quantity of the extrudate pieces (26.5 mL)was mixed with about 10 mL of inert Alundum and charged to a tubularreactor described herein in Example 2 and heated to about 149° C. andtreated with hydrogen at an initial flow rate of 5 mL/min that wasincreased to 25 mL/min. After about two hours, the reactor was purgedwith nitrogen followed by the introduction of a hydrocarbon-containingfluid feed.

Catalyst B: (MoHPA/SiO₂) A solution of 3.50 grams of12-molybdophosphoric acid in about 25 mL of distilled water was preparedand added to a 5.7 gram quantity of Davison grade 57 silica underincipient wetness conditions. The resulting material was dried in avacuum oven at about 85° C. for about 17 hours to provide a final weightof 8.67 grams (9.2 grams theoretical). A portion of the resulting driedmaterial (4.0 grams) was mixed with 2.0 grams of bentonite clay fillerand enough distilled water was added to make a paste sufficient toextrude through a 25 mL plastic syringe. The extrudate was then dried ina drying oven at about 115° C. for about two hours. The resulting driedextrudate was then granulated to provide pieces of about 0.125 inches toabout 0.25 inches in length. A 5.34 gram quantity of the extrudatepieces was mixed with about 10 mL of inert Alundum and charged to atubular reactor described herein in Example 2 and heated to about 121°C. and treated with hydrogen at an initial flow rate of 5 mL/min thatwas increased to 25 mL/min. After about three hours, the reactor waspurged with nitrogen followed by the introduction of ahydrocarbon-containing fluid feed.

Catalyst C: (MoHPA/ZnCl₂ (10%) on alumina) In separate beakers,solutions of 2.45 grams of 12-molybdophosphoric acid in about 25 mL ofdistilled water and 2.24 grams of zinc chloride in about 25 mL ofdistilled water were prepared and added (in three portions) to an 11.37gram quantity of alumina (Condea Pural SB-1) under incipient wetnessconditions. The resulting material was dried in a vacuum oven at about80° C. between additions. After the final loading, the resultingmaterial was dried in a vacuum oven at about 60° C. for about 18 hoursto provide a final weight of 14.79 grams. The resulting dried materialwas then moistened with enough distilled water to provide a paste thatwas extruded through a 25 mL plastic syringe. The resulting extrudatewas then dried in a vacuum oven at about 60° C. for about 18 hours. Theresulting dried extrudate was then granulated to provide pieces of about0.125 inches to about 0.25 inches in length. A 14.15 gram quantity ofdried extrudate was obtained. A 6.07 gram quantity of the extrudatepieces (10 mL) was mixed with about 10 mL of inert Alundum and chargedto a tubular reactor described herein in Example 2 and heated to about139° C. and treated with hydrogen at an initial flow rate of 5 mL/minthat was increased to 25 mL/min. After about four hours, the reactor waspurged with nitrogen followed by the introduction of ahydrocarbon-containing fluid feed.

Catalyst D: (MoHPA/ZnCl₂ (2%) on alumina) In separate beakers, solutionsof 2.77 grams of 12-molybdophosphoric acid in about 10 mL of distilledwater and 0.37 grams of zinc chloride in about 10 mL of distilled waterwere prepared and added in three portions to a 13.37 gram quantity ofalumina (Condea Pural SB-1) under incipient wetness conditions. Theresulting material was dried in a vacuum oven at about 80° C. betweenadditions. After the final loading, the resulting material was dried ina vacuum oven at about 60° C. for about 18 hours and reweighed. Afterweighing, enough water was added to provide a paste that was extrudedthrough a 25 mL plastic syringe. The resulting extrudate was then driedin a vacuum oven at about 60° C. for about 18 hours. The resulting driedextrudate was then granulated to provide pieces of about 0.125 inches toabout 0.25 inches in length. A 14.03 gram quantity of dried extrudatewas obtained. A 10.25 gram quantity of the extrudate pieces (20 mL) wasmixed with about 10 mL of inert Alundum and charged to a tubular reactordescribed herein in Example 2 and heated to about 260° C. and treatedwith hydrogen at an initial flow rate of 5 mL/min that was increased to25 mL/min. After about three hours, the reactor was purged withnitrogen.

EXAMPLE 2

This example illustrates the use of the catalyst compositions describedherein in Example 1 as catalyst compositions in a process comprisingcontacting an isoparaffin and a C₅ olefin.

The reactor system consisted of a syringe pump for delivering ahydrocarbon-containing fluid feed, a tubular reactor (0.75 inch diameterand 18 inches length, with a thermowell in the center), back-pressureregulators, sampling components, and product collection equipment. Thehydrocarbon-containing fluid feed was drawn into the syringe pump, thenpumped downflow across the catalyst bed (centered in the reactor withinert Alundum below and above the active catalyst bed; each separated byglass wool). The reactor was contained inside an electrically heatedfurnace, the temperature of which was set and monitored independentlyfrom the reactor bed temperature disclosed in the Tables.

After a Time On Stream (TOS) as indicated in Table 1, each catalystcomposition was subjected to a regeneration comprising a hydrogentreatment according to the following process. The hydrocarbon-containingfluid feed was stopped and the reactor was drained of liquid components.After purging the reactor for about 10 minutes with nitrogen, thetemperature set point was increased from 300° F. to 350° F. Hydrogenflow was started at a rate of 25 standard cubic centimeters per minute(sccm) and increased to 50 sccm over the course of two hours and thenstopped. The flow of nitrogen was then started at 50 sccm and allowed toflow for about 18 hours

Table 1 discloses a comparison of the results obtained utilizingcatalyst compositions A, B and C described herein in Example 1. Theresults disclose that catalyst composition C comprising12-molybdophosphoric acid, zinc, and a support component comprisingalumina provided for an increase in C6–C8 and C9 components compared tocatalyst compositions A and B. Such components are valuable as gasolinecomponents and have lower vapor pressure than the parent C5 olefins.Catalyst composition C also provided for a decrease in C10+ componentscompared to catalyst compositions A and B. Such components cannegatively influence gasoline distillation index (DI) values byincreasing the T50 and T90 values. Catalyst composition C also providedfor an increase in total 2-butenes compared to catalyst compositions Aand B. The 2-butenes are valuable components for alkylation feeds, andhigh octane, low vapor pressure alkylate can be prepared from such2-butenes. In addition, catalyst composition C provided for an 87.5%restoration of activity after the catalyst regeneration (hydrogentreatment). The restoration of activity was based on the extent ofconversion obtained after the catalyst regeneration as a percentage ofthe extent of conversion obtained with a fresh catalyst composition. Noresponse was noted for catalyst composition B when subjected to the samehydrogen treatment.

TABLE 1 A B C (MoHPA/ (MoHPA/ (MoHPA/ Catalyst Zeo B/Pt) SiO2)Al2O3/ZnCl2) % MoHPA 18.2 40 15.3 % Pt 0.6 0 0 % ZnCl2 0 0 13.9 TOS, Hrs7.5 4 4 Rxtr Temp., ° F. 272 251.4 315 Feed (wt %) Lights 0.15 0 0.308iC5 49.49 49.33 49.77 1C5 = 25.31 25.35 25.12 iC5 = 24.05 25.32 23.50nC5 0.25 0.00 0.25 2C5 = 0.00 0.00 0.04 C6+ 0.75 0.00 1.00 Product (wt%) C3 0.000 0.000 0.000 iC4 0.040 0.030 0.063 nC4 0.000 0.000 0.050 C3 =0.000 0.000 0.002 1C4 =/iC4 = 0.030 0.110 0.317 2C4 = 0.000 0.000 0.127iC5 50.83 50.82 53.06 nC5 0.29 0.03 0.27 C5 = 24.48 33.298 36.81 C6–C80.91 1.13 1.95 C9 0.43 0.96 2.97 C10+ 22.02 13.59 4.08 1C5 = Conversion75.28 57.95 36.88 iC5 = Conversion 71.73 58.98 44.65 % Activity Restored100 No Response 87.5 After Hydrogen Treatment MoHPA =12-Molybdophosphoric acid Zeo B = Zeolite Beta 1C4 =/iC4 = is total ofboth components

EXAMPLE 3

Example 3 illustrates a process of the present invention utilizingcatalyst composition C (MoHPA/ZnCl₂ (10%) on alumina) described hereinin Example 1. The reactor system described herein in Example 2 wasutilized. The process was initially conducted over a time period ofabout six hours. The hydrocarbon-containing fluid feed utilized inExample 3 comprised the C5 fraction from fluidized catalytically cracked(FCC) gasoline utilizing model compounds. The composition of thehydrocarbon-containing fluid feed utilized in Example 3 is disclosedherein in Table 2. Table 3 discloses the 1-pentene (1C5=) conversion,2-methyl-2-butene (2MB2) conversion, and the reactor temperature afterthree, four and six hour time periods on stream. The results disclosedin Table 3 are disclosed graphically herein in FIG. 1. After six hours,catalyst composition C was subjected to a first regeneration accordingto the following process. The hydrocarbon-containing fluid feed wasstopped and the reactor was drained of liquid components. After purgingthe reactor for about 10 minutes with nitrogen, the temperature setpoint was increased from 300° F. to 350° F. Hydrogen flow was started ata rate of 25 standard cubic centimeters per minute (sccm) and increasedto 50 sccm over the course of two hours and then stopped. The flow ofnitrogen was then started at 50 sccm and continued for about 18 hours.After the first regeneration, the process was continued forapproximately six hours. Table 4 discloses the 1-pentene (1C5=)conversion, 2-methyl-2-butene (2MB2) conversion, and the reactortemperature after three, four, five, and six hour time periods on streamafter the first regeneration. The results disclosed in Table 4 aredisclosed graphically herein in FIG. 2. After the six hour run after thefirst regeneration, catalyst composition C was subjected to a secondregeneration similar to the first regeneration except the temperatureset point was increased to 500° F. to provide a catalyst compositiontemperature of about 530° F. Catalyst composition C was subjected to asecond regeneration according to the following process. Thehydrocarbon-containing fluid feed was stopped and the reactor wasdrained of liquid components. After purging the reactor for about 10minutes with nitrogen, the temperature set point was increased from 300°F. to 500° F. to provide a catalyst composition temperature of about530° F. Hydrogen flow was started at a rate of 25 standard cubiccentimeters per minute (sccm) and increased to 50 sccm over the courseof two hours and then stopped. The flow of nitrogen was then started at50 sccm and continued for about 18 hours. After the second regeneration,the process was continued for approximately six hours. Table 5 disclosesthe 1-pentene (1C5=) conversion, 2-methyl-2-butene (2MB2) conversion,and the reactor temperature after four, five, and six hour time periodson stream after the second regeneration. The results disclosed in Table5 are disclosed graphically herein in FIG. 3.

The data disclosed herein in Tables 3, 4, and 5 clearly demonstrate thatcatalyst composition C demonstrated good regenerability after the firstregeneration, but the second regeneration had less of an impact onrestoring catalyst composition activity.

TABLE 2 Feed C3 = 0.000 iC4 0.146 iC4 = 0.000 nC4 0.049 2C4 = t 0.000NeoC5 0.113 2C4 = c 0.000 3MB1 0.000 iC5 49.772 1C5 = 25.118 2MB1 1.489nC5 0.251 2C5 = t 0.028 2C5 = c 0.015 2MB2 22.010 ?C1–C5 0.006 C6–C80.840 C9 0.073 C10+ 0.087 Total 99.996

TABLE 3 TOS, hours 3 4 6 1C5 = Conversion 69.45 36.88 30.49 2MB2Conversion 73.23 44.65 36.61 Reactor Temp., ° F. 315.2 314 312.2

TABLE 4 Time On Stream, hours after first regeneration 3 4 5 6 1C5 =Conversion 60.8 49.1 49.2 49.61 2MB2 Conversion 45.51 33.64 26.73 30.39Reactor Temp., ° F. 367.2 369.1 368.1 366.5

TABLE 5 Time On Stream, hours after second regeneration 4 5 6 1C5 =Conversion 26.09 27.52 25.48 2MB2 Conversion 15.45 15.08 13.59 ReactorTemp., ° F. 366.9 366.7 368.2

EXAMPLE 4

Example 4 illustrates a process of the present invention comprising theaddition of an organic chloride compound.

Catalyst composition D (MoHPA/ZnCl₂ (2%) on alumina) described herein inExample 1 and the reactor system described herein in Example 2 wereutilized. Catalyst composition D was pre-treated by heating to 500° F.under a flow of hydrogen at a flow rate of 25 standard cubic centimetersper minute (sccm) and a flow of an organic chloride compound comprisinga mixture of tetrachloroethylene (TCE) and ethylaluminum dichloride(EADC) at a flow rate of 20 microliters per hour for about 2 hours. TheTCE/EADC mixture, comprising 100 mL tetrachloroethylene (TCE) and 80microliters of pure ethylaluminum dichloride (EADC) prepared beforehandin an inert atmosphere enclosure, was charged to a syringe-type pumpunder a nitrogen atmosphere and the flow rate of the pump was adjustedto deliver the 20 microliters per hour flow to the reactor. The hydrogenand organic chloride compound flows were then stopped. The temperatureset point was reduced to 350° F. and the hydrocarbon-containing fluidfeed was then introduced when the top of the catalyst bed was 335° F.The process was initially conducted over a time period of about fourhours. The composition of the hydrocarbon-containing fluid feed isdisclosed herein in Table 6. Table 6 discloses the composition of theinitial hydrocarbon-containing fluid feed as well as the composition ofthe hydrocarbon-containing fluid feed that was adjusted after about 10hours total time on stream during a process of the present invention.

Table 7 discloses the results obtained after two, three, and four hourtime periods on stream. Table 7 discloses the 1-pentene (1C5=)conversion, 2-methyl-2-butene (2MB2) conversion, the reactortemperature, and temperature set point (TSP). No organic chloridecompound was added during the first four hours on stream. The resultsdisclosed in Table 7 are disclosed graphically herein in FIG. 4. Afterabout four hours, catalyst composition D was subjected to a firstregeneration according to the following process. Thehydrocarbon-containing fluid feed was stopped and the reactor wasdrained of liquid components. After purging the reactor for 10 minuteswith nitrogen, the temperature set point was increased from 350° F. to500° F. Hydrogen flow was then started at a rate of 25 sccm along withan organic chloride compound comprising a mixture of tetrachloroethylene(TCE) and ethylaluminum dichloride (EADC) added at a rate of 20microliters per hour. The TCE/EADC mixture, prepared beforehand asdescribed herein, was charged to a syringe-type pump under a nitrogenatmosphere and the flow rate of the pump was adjusted to deliver the 20microliters per hour flow to the reactor. After about 2.5 hours, thehydrogen and organic chloride compound flows were stopped. Nitrogen flowwas then started at 50 seem and the nitrogen flow was maintained forabout 18 hours with the temperature set point reduced to 350° F.

After the first regeneration, the process was continued for about sixhours. During the six hours on stream after the first regeneration(hydrogen treatment), an organic chloride compound comprising a mixtureof tetrachloroethylene (TCE) and ethylaluminum dichloride (EADC) wasadded at a rate of 20 microliters per hour. The TCE/EADC mixture,comprising 100 mL tetrachloroethylene (TCE) and 80 microliters of pureethylaluminum dichloride (EADC) prepared beforehand in an inertatmosphere enclosure, was charged to a syringe-type pump under anitrogen atmosphere and the flow rate of the pump was adjusted todeliver the 20 microliters per hour flow to the reactor. Table 8discloses the 1-pentene (1C5=) conversion, 2-methyl-2-butene (2MB2)conversion, reactor temperature, organic chloride compound (Cl) feedrate, and temperature set point at one hour intervals over the six hourtime period on stream after the first regeneration. The resultsdisclosed in Table 8 are disclosed graphically herein in FIG. 5. Afterabout six hours time on stream after the first regeneration, thehydrocarbon-containing fluid feed was adjusted to utilize ahydrocarbon-containing fluid feed composition as described herein inTable 6 under Feed #2.

After about six hours time on stream after the first regeneration (afterabout 10 hours total time on stream) catalyst composition D wassubjected to a second regeneration similar to the first regenerationexcept the temperature set point was held at 400° F. and no organicchloride compound was added. Catalyst composition D was subjected to thesecond regeneration according to the following process. Thehydrocarbon-containing fluid feed was stopped and the reactor wasdrained of liquid components. After purging the reactor for 10 minuteswith nitrogen, the temperature set point was increased from 350° F. to400° F. Hydrogen flow was then started at a rate of 25 sccm. After about2.5 hours, the hydrogen flow was stopped. Nitrogen flow was then startedat 50 sccm and the nitrogen flow was maintained for about 18 hours withthe temperature set point reduced to 350° F.

After the second regeneration, the rate of organic chloride compoundaddition comprising the mixture of tetrachloroethylene (TCE) andethylaluminum dichloride (EADC) was increased to 40 microliters per hourand the process was continued for about six hours. Table 9 discloses the1-pentene (1C5=) conversion, 2-methyl-2-butene (2MB2) conversion,reactor temperature, organic chloride compound (Cl) feed rate, andtemperature set point at one-hour intervals over the additional six hourtime period on stream after the second regeneration. The resultsdisclosed in Table 9 are disclosed graphically herein in FIG. 6.

TABLE 6 Feed #1 Feed #2 C2 0.000 0.000 C3 0.000 0.000 iC4 0.038 0.040iC4 = 0.000 0.000 nC4 0.052 0.048 2C4 = t 0.000 0.000 NeoC5 0.125 0.1182C4 = c 0.000 0.000 3MB1 0.000 0.000 iC5 52.564 50.305 1C5 = 23.91224.988 2MB1 1.457 1.571 nC5 0.267 0.290 2C5 = t 0.000 0.014 2C5 = c0.000 0.012 2MB2 20.964 21.924 ?C1–C5 0.000 0.000 C6–C8 0.620 0.690 C90.000 0.000 C10+ 0.000 0.000 Total 100.000 100.000

TABLE 7 (No Organic Chloride Compound Addition) TOS, hours 2 3 4 1C5 =Conversion 16.54 15.26 11.47 2MB2 Conversion 2.15 2.86 2.16 Reactor, °F. 366.3 363.9 362.2 C1 Feed Rate 0 0 0 Temp. Set Point, ° F. 350 350350

TABLE 8 (20 microliter/hour Organic Chloride Compound Addition) Time OnStream, hours after first regeneration and beginning of 20 microliter/hrchloride addition 1 2 3 4 5 6 1C5 = 5.62 4.17 3.77 2.36 — 1.33Conversion 2MB2 1.15 0.88 0.55 0.29 — 0 Conversion Reactor, ° F. 368.5366.7 367.6 363.2 364.7 414.4 Cl Feed Rate 20 20 20 20 20 20 Temp. Set350 350 350 350 350 400 Point, ° F.

TABLE 9 (40 microliter/hour Organic Chloride Compound Addition) Time OnStream, hours after second regeneration and beginning of 40microliter/hr chloride addition 1 2 3 4 5 6 1C5 = 26.18 23.41 20.2517.41 14.13 11.91 Conversion 2MB2 1.52 1.62 1.4 1.35 1.11 0.96Conversion Reactor, ° F. 512.3 509 509.7 506.4 506.8 506.6 Cl Feed Rate40 40 40 40 40 40 Temp. Set 475 475 475 475 475 475 Point, ° F.

The results disclosed herein in Example 4 clearly demonstrate that therate of catalyst deactivation can be diminished utilizing a process ofthe present invention comprising the addition of an organic chloridecompound. Comparing the results disclosed in Tables 7 and 9 (disclosedgraphically in FIGS. 4 and 6, respectively), the rate of decline incatalyst composition activity is very similar even though the reactortemperatures for the data in Table 9 (FIG. 6) are approximately 140° F.higher than the reactor temperatures for the data in Table 7 (FIG. 4).In addition, comparing the results disclosed in Tables 8 and 9(disclosed graphically in FIGS. 5 and 6, respectively) show that keepingthe reactor temperature less than or equal to about 425° F. improves therestorative effects of the regenerations similar to the resultsdisclosed herein in Example 3 (results disclosed in Tables 3, 4, and 5and respective associated FIGS. 1, 2, and 3).

The results shown in the above examples clearly demonstrate that thepresent invention is well adapted to carry out the objects and obtainthe ends and advantages mentioned as well as those inherent therein.

Reasonable variations, modifications, and adaptations can be made withinthe scope of the disclosure and the appended claims without departingfrom the scope of the present invention.

1. A process of preparing a catalyst composition comprising contacting asupport component with a heteropoly acid and a zinc component andfurther wherein said contacting is selected from the group consisting ofimpregnating, mixing, and combinations thereof; wherein said process ofpreparing said catalyst composition further comprises activating underan activating condition comprising: a temperature in the range of fromabout 50° C. to about 500° C.; a pressure in the range of from about 0pounds per square absolute to about 750 pounds per square inch absolute;and a time period in the range of from about 0.1 hour to about 30 hours;and wherein said activating condition further comprises an atmospherecomprising: 1) a reducing agent selected from the group consisting ofhydrogen, hydrogen diluted with nitrogen, ammonia, hydrazine, otherreducing gases, and combinations thereof, and 2) an organic chloridecompound selected from the group consisting of tetrachloroethylene,ethylaluminum dichloride, carbon tetrachloride, hexachloroethane,1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane,2-chloro-2-methylpropane, and combinations thereof.
 2. A processaccording to claim 1 wherein said impregnating is selected from thegroup consisting of incipient wetness impregnation, spray impregnation,and combinations thereof.
 3. A process according to claim 1 wherein saidprocess of preparing said catalyst composition further comprises, aftersaid impregnating, subjecting to a means for forming to provide for aformed mixture comprising heteropoly acid, zinc, and support component.4. A process according to claim 3 wherein said means for forming isselected from the group consisting of means for extruding, means forgranulating, means for agglomerating, and combinations thereof.
 5. Aprocess according to claim 3 wherein said means for forming comprises ameans for extruding to provide an extrudate comprising heteropoly acid,zinc, and support component.
 6. A process according to claim 3 whereinsaid means for forming comprises a means for granulating to provide agranulate comprising heteropoly acid, zinc, and support component.
 7. Aprocess according to, claim 3 wherein said means for forming comprises ameans for agglomerating to provide an agglomerate comprising heteropolyacid, zinc, and support component.
 8. A process according to claim 1wherein said process of preparing said catalyst composition furthercomprises drying under a drying condition comprising: a temperature inthe range of from about 20° C. to about 90° C.; a pressure in the rangeof from about 0 pounds per square inch absolute to about 200 pounds persquare inch absolute; and a time period in the range of from about 0.5hours to about 40 hours.
 9. A process according to claim 8 wherein saiddrying condition further comprises an atmosphere comprising air.
 10. Aprocess according to claim 1 wherein said process of preparing saidcatalyst composition further comprises calcining under a calciningcondition comprising: a temperature in the range of from about 100° C.to about 500° C.; a pressure in the range of from 0 pounds per squareinch absolute to about 750 pounds per square inch absolute; and a timeperiod in the range of from about 0.5 hours to about 30 hours.
 11. Aprocess according to claim 10 wherein said calcining condition furthercomprises an atmosphere selected from the group consisting of anoxygen-containing atmosphere, nitrogen, helium, argon, and combinationsthereof.
 12. A process according to claim 1 wherein said organicchloride compound comprises tetrachloroethylene.
 13. A process accordingto claim 1 wherein said heteropoly acid is selected from the groupconsisting 12-molybdophosphoric acid, 12-tungstophosphoric acid,molybdosilicic acid, 12-tungstosilicic acid, and combinations thereof.14. A process according to claim 13 wherein said heteropoly acid is12-molybdophosphoric acid.
 15. A process according to claim 1 whereinsaid zinc component is selected from the group consisting of zincbromide, zinc chloride, zinc iodide, zinc nitrate hydrate, zinc nitratehexahydrate, zinc nitrate, zinc oxide, zinc perchlorate hexahydrate,zinc sulfate heptahydrate, and combinations thereof.
 16. A processaccording to claim 15 wherein said zinc component is zinc chloride. 17.A process according to claim 1 wherein said support component isselected from the group consisting of alumina, silica, aluminasilicates,activated carbon, zeolites, oxides of the metals of Groups II, III, IV,V, and VI A of the Periodic Table of the Elements, and combinationsthereof.
 18. A process according to claim 1 wherein said supportcomponent is alumina.
 19. A process according to claim 1 wherein aweight percent of polyatom based on the total weight of said catalystcomposition is in the range of from about 0.1 to about
 10. 20. A processaccording to claim 19 wherein said polyatom comprises molybdenum.
 21. Aprocess according to claim 1 wherein a weight percent of zinc based onthe total weight of said catalyst composition is in the range of fromabout 0.1 to about
 10. 22. A process according to claim 1 wherein aweight percent of said support component based on the total weight ofsaid catalyst composition is in the range of from about 50 to about99.9.
 23. A composition prepared by the process of claim
 1. 24. Acomposition prepared by the process of claim
 3. 25. A compositionprepared by the process of claim
 8. 26. A composition prepared by theprocess of claim
 10. 27. A composition prepared by the process of claim13.
 28. A composition prepared by the process of claim
 15. 29. Acomposition prepared by the process of claim
 17. 30. A compositionprepared by the process of claim
 19. 31. A composition prepared by theprocess of claim 20.